A family of oxychloride amorphous solid electrolytes for long-cycling all-solid-state lithium batteries

Solid electrolyte is vital to ensure all-solid-state batteries with improved safety, long cyclability, and feasibility at different temperatures. Herein, we report a new family of amorphous solid electrolytes, xLi2O-MCly (M = Ta or Hf, 0.8 ≤ x ≤ 2, y = 5 or 4). xLi2O-MCly amorphous solid electrolytes can achieve desirable ionic conductivities up to 6.6 × 10−3 S cm−1 at 25 °C, which is one of the highest values among all the reported amorphous solid electrolytes and comparable to those of the popular crystalline ones. The mixed-anion structural models of xLi2O-MCly amorphous SEs are well established and correlated to the ionic conductivities. It is found that the oxygen-jointed anion networks with abundant terminal chlorines in xLi2O-MCly amorphous solid electrolytes play an important role for the fast Li-ion conduction. More importantly, all-solid-state batteries using the amorphous solid electrolytes show excellent electrochemical performance at both 25 °C and −10 °C. Long cycle life (more than 2400 times of charging and discharging) can be achieved for all-solid-state batteries using the xLi2O-TaCl5 amorphous solid electrolyte at 400 mA g−1, demonstrating vast application prospects of the oxychloride amorphous solid electrolytes.


Response to the Reviewers' Comments (Manuscript NCOMMS-22-47305-T)
We are very grateful for the reviewers' constructive comments and insightful suggestions for improving the quality of this manuscript. During the revision, we have carried out additional experiments and literature review to gain a better understanding of the oxychloride amorphous solid electrolytes. As a result, we have updated 1 figure in the revised manuscript. More convincing discussions, experiment details, and references have also been added in the appropriate parts of the revised manuscript. Besides, 3 figures have been added and 1 figure have been updated in the revised supplementary information.
The major experiments and updates include: 1. In response to the suggestions of Reviewer #1, we have supplied the operational stack pressure for all batteries, detailed information for NCM83, and the fabrication details for all-solid-state pouch cell. We have also highlighted the LCO all-solid-state batteries by providing cell configurations or bolding the text. Additionally, we have updated the discussions towards the structure disorder and Ea_LT < Ea_HT by reviewing more references.
2. In addressing the comments of Reviewer #2, we have elucidated the effects of oxygen incorporation through the synthesis of Li-Ta-Cl materials and characterization of their phase compositions and ionic conductivities. We have also conducted DC measurements under ion-blocking and electron-blocking conditions to identify the electronic conductivity and Li-ion conductivity of our reported oxychloride solid electrolytes. The electrochemical stability windows were provided through doing the LSV test. Moreover, after checking relevant references, we have determined that our reported solid electrolytes strictly belong to amorphous state, and have made the necessary changes to our corresponding descriptions.
The following are our point-by-point responses to the questions/comments raised by each reviewer.
The revisions made in the revised manuscript and supplementary information are indicated and highlighted in yellow for clarity and ease of reference.
We deeply appreciate the opportunity of revising the manuscript.
Many thanks again! 1. The operational stack pressure should be mentioned for all batteries. Only the fabrication pressures are mentioned in Method for now.

Response:
We highly thank the reviewer for this suggestion. The operational stack pressure used for all the batteries in this manuscript was ~80 MPa. This value is within the range of a typical stack pressure for inorganic electrolyte-based all-solid-state batteries (Science, 2021, 373, 1494-1499; Nat. Energy 2022, 7, 83-93 (using ~250 MPa)).

Revision made:
We have added the stack pressure information in the Method part of the revised manuscript.
Page 22 in the revised manuscript: '…The obtained internal pellet cell was sandwiched between two stainless-steel rods as current collectors. Finally, a stack pressure of ~80 MPa was applied to the solid cell for various electrochemical tests. All cell fabrication processes were carried out in an Ar-filled glove box (H2O, O2 <0.1 ppm)…' 2. It's mentioned LCO is used in Method, but all batteries I see are by NMC83.

Response:
We thank the reviewer for this comment. Two types of cathode materials were used in this work: NMC83 and LCO. NMC83 ASSBs were demonstrated in Fig. 5a-e and Supplementary Fig. 17, as well as NMC83 pouch cell in Supplementary Fig. 19. The performance of LCO ASSBs were exhibited in Fig. 5f-g and Supplementary Fig. 18. We double-checked the whole manuscript and supplementary information files. Indeed, the depicted cathodes in the manuscript and supplementary information were not very visually distinct. In order to highlight the different cathode materials used in each battery, we added detailed cell configurations in Fig. 5 in the revised manuscript. We also bolded the text of "LCO" in Supplementary Fig. 18 of the revised supplementary information.
Revision made: We added detailed cell configurations in Fig. 5 in the revised manuscript. We also bolded the text of "LCO" in Supplementary Fig. 18

Response:
We thank the reviewer for this question. NCM83 (LiNi0.83Co0.11Mn0.06O2) cathode active material we used in this work is provided by China Automotive Battery Research Institute Co, Ltd. They are polycrystalline (PC) particles with a size around 3 μm. The SEM images of the NCM83 particles are shown in Figure R1. Figure R1 SEM images of the NCM83 cathode material.

Revision made:
We have added detailed information of NCM83 in the Method part of the revised manuscript.
Page 22 in the revised manuscript: '…10 mg of amorphous SE/NCM83 composite (3:7 mass ratio) was uniformly spread onto the surface of the one side of electrolyte layer and pressed with ~360 MPa for 5 minutes. NCM83 (LiNi0.83Co0.11Mn0.06O2) cathode material (polycrystalline particle size: ~3 μm) was provided by China Automotive Battery Research Institute Co, Ltd. Subsequently, Li-In alloy was placed on the other side of the…' 4. It's nice to see a pouch cell in SI. But more details should be provided, as it's not mentioned in Method, i..e, cathode loading, separator thickness, slurry casting?, layer by layer?, operational pressure, sealing, etc Response: We highly thank the reviewer for this comment. During the revision process, we have added the detailed information about the pouch cell fabrication in the Method part of the revised manuscript.

Revision made:
We have added detailed information about the pouch cell fabrication and one reference in the revised manuscript. The all-solid-state pouch cell was fabricated by stacking layers of NCM83/1.6Li2O-TaCl5 cathode, SE separators (Li3YCl6 and 1.6Li2O-TaCl5), and Li-In alloy anode. The membranes of cathode composites and SEs were made by dry-film processing method 59 , where 0.5 wt% Polytetrafluoroethylene (PTFE) were added to induce the formation of doughs and followed by calendaring to the target thickness (~80 um). The loading of the cathode was 13.125 mg cm -2 . Stacking each layers was completed in the Ar-filled glovebox, which was then sealed in plastic vacuum bag and for transferring to a dry room for further packing in the aluminum-plastic bag. A pressure of ~10 MPa was applied on the pouch cell during the cycling performance test using Neware battery testing system.' Page 30 in the revised manuscript:  (2022))? A brief discussion of the mechanism along this direction will further benefit the readers.

Response:
We highly appreciate the reviewer for the question and suggestion! 7 Li spin-lattice relaxation (SLR) NMR measurements can provide the activation energies not only corresponding to short-range (local motions) but also the long-range lithium-ion diffusions in bulk electrolytes. In this method, the SLR rate (R = 1/T1, T1 is the spin-lattice relaxation time) is recorded as a function of the temperature which depends on the fluctuation of the local magnetic field resulting from the motions of Li ions. These fluctuations are described by correlation function G(t) characterizing the correlation time, which is related to the Li-ion jump rates between two successive jumps. Most importantly, the SLR rate is related to the G(t) through the spectral density function which is the Fourier transform of G(t) (J. Electroceramics 2017, 38, 142-156;MRS Bull. 2009, 34, 915-922).
In general, the diffusion-induced rate increases with increasing temperature (lowtemperature flank) until it reaches a maximum followed by a decrease of R with further increasing temperature (high-temperature flank) ( Fig. 2f and g in the manuscript). Since the correlation time exhibits an Arrhenius behavior, the slopes of the plot of 1/T1 vs 1/T can be used to determine the activation energies for Li-ion transport in long-range (Ea HT ) and short-range (Ea LT ) from the hightemperature flank and low-temperature flank, respectively (ChemPhysChem 2012, 13, 53-65). The Ea LT characterizes elementary jump processes, while Ea HT probes long-range or "bulk" Li-ion diffusions. (J. Am. Chem. Soc. 2016, 138, 11192-11201;Phys. Chem. Chem. Phys. 2013, 15, 7123-7132) The Bloembergen, Purcell, and Pound (BPP) model used to study the fluctuation of the internal fields predicts a symmetric rate peak with an asymmetry parameter, β = 2 which does not consider the correlation effects such as Coulomb interactions (repulsive/attractive) and/or structural disorders. The Ea HT and Ea LT are related to each other by a relationship Ea LT = (β -1) Ea HT where 1 < β ≤ 2 (Phys. Rev. 1948, 73, 679-712). In the present cases, β values were determined to be 1.34 and 1.68 for the 1.6Li2O-TaCl5 and the 1.5Li2O-HfCl4 samples, respectively, showing that the Ea LT is lower than Ea HT for each case. Asymmetric rate peaks are often found for structurally complex ion conductors (Phys. Chem. Chem. Phys. 2019, 21, 8489-8507;J. Phys. Chem. Lett. 2013, 4, 2118-2123ACS Appl. Mater. Interfaces 2018, 10, 33296-33306). The deviation from the BPP model often occurs in the low-temperature regime as the local hopping of Li ions is affected by the correlation effects, leading to a reduced Ea LT value comparatively (ChemPhysChem 2012, 13, 53-65).
Deviation from the BPP model (1 < β < 2) can be explained by correlation effects such as Coulomb interactions (repulsive/attractive), correlated ion dynamics, and/or structural disorders. For the amorphous oxychloride samples 1.6Li2O-TaCl5 and 1.5Li2O-HfCl4, the Li ions are exposed to an irregularly formed time-dependent potential landscape while diffusing. However, due to the challenges of completely understanding the structure of amorphous solids, we currently may not be able to elaborate on the correlation effects towards the β value deviation. Therefore, broadly speaking, we ascribed the reason for the lower Ea LT to the inherited structural disorder.
The paper mentioned by the reviewer (Adv. Mater. 2022, 34, 2207411) reported that in a typical sulfide electrolyte, Li-ion conduction can be boosted by the anharmonic coupling of lowfrequency Li phonon modes with high-frequency anion stretching or flexing phonon modes. The results were obtained by ab initio computation in a temperature range of 0-300 K. Comparing to the paddle-wheel phenomenon that mostly analyzed under high temperature, the results talked about in this paper (Adv. Mater. 2022, 34, 2207411) is more relevant to the practical operating temperatures of solid-state batteries. However, in our studies about 7 Li SLR-NMR for SEs, any couplings of the spins with phonons or conduction electrons were considered negligible (J. Am. Chem. Soc. 2022, 144, 1795−1812Phys. Rev. B 2008, 77, 024311). Therefore, from this perspective, it is hard to directly link our 7 Li SLR-NMR results with phonon coupling to explain the factors towards the Li-ion transport, but we still can provide some additional discussion to clarify our adopted method and results.

Revision made:
We have updated the following sentences and references in the revised manuscript.
Page 8-9 in the revised manuscript: '…In the present cases, β values were determined to be 1.34 and 1.68 for the 1.6Li2O-TaCl5 and the 1.5Li2O-HfCl4 samples, respectively, indicating structurally complex Li-ion conductions. [40][41][42] Generally, correlation effects (e.g., Coulomb interactions, correlated ion dynamics, structural disorders, etc.) are considered closely associated with the impacted Li-ion conduction. 43,44 In our studies of 7 Li SLR NMR for the amorphous SEs, the native structural disorder of the two amorphous samples was regarded as the major contributor towards the deviation of β value off 2 (1 < β < 2), leading to smaller Ea LT values compared to those of Ea HT . 33,42 Elaboration on the relevant correlation effects of locally disordered structure on the Li-ion migration is proposed as an interesting research direction that appeals to further attention.' Page 28-29 in the revised manuscript: Reference: In such a sense, how about the conductivity of the material in the LiCl-TaCl5 system? By comparing the behavior of the LiCl-TaCl5 system, the effect of oxygen incorporation can be discussed.

Response:
We highly appreciate the reviewer for the question, which deepens the mechanism understanding of this manuscript. During the revision, we synthesized a series of Li-Ta-Cl materials (LiTaCl6, Li2TaCl7, Li3.2TaCl8.2, and Li4TaCl9) following the same experimental procedure for xLi2O-TaCl5. The stoichiometric amounts of precursors TaCl5 and LiCl were milled using a high-speed ball milling machine at 500 rpm for 10 h. Figure R2 shows the XRD patterns of the as-prepared Li-Ta-Cl system. Except for the LiCl and TaCl5 impurities, the as-synthesized Li-Ta-Cl phase seemed to be amorphous. With an increasing LiCl content, the diffraction peak of the LiCl impurity became more prominent. In comparison, the Li-Ta-O-Cl system can remain amorphous for a similar range of Li/Ta ratios of 2.2 to 3.6 for xLi2O-TaCl5 (x = 1.1-1.8). We further obtained the ionic conductivities of above compounds by electrochemical impedance spectroscopy (EIS) method ( Figure R3). The room-temperature (RT) ionic conductivities of LiTaCl6, Li2TaCl7, Li3.2TaCl8.2, and Li4TaCl9 were 8.81 × 10 -8 , 2.81 × 10 -7 , 3.92 × 10 -7 , and 7.20 × 10 -7 S cm -1 , respectively. Apparently, increasing the molar ratio of LiCl in the starting materials helped to improve the overall ionic conductivity of the Li-Ta-Cl samples. However, the values were still limited to the 10 -7 S cm -1 level, which were 4 orders of magnitude lower than those of the Li-Ta-O-Cl system with O incorporation. Furthermore, the activation energies of Li-Ta-Cl materials were all above 0.5 eV (Figure R4), which were much higher than those of the Li-Ta-O-Cl amorphous SEs.

Figure R2
Lab-based XRD patterns for the as-prepared LiTaCl6, Li2TaCl7, Li3.2TaCl8.2, and Li4TaCl9 samples. The hump between 10 o and 30 o is due to the Kapton film which was used to protect the samples from air exposure.
Based on above results, we generally conclude three main effects of incorporating O in our Li-Ta-O-Cl amorphous SEs:

1) Moderate amount of O incorporation benefits to rearrange the Li-Ta-O-Cl frameworks and contributes to the amorphization of Li-Ta-O-Cl
. Similar result can also be found in the Si2Odoped Li2S-B2S3-LiI system (Adv. Energy Mater. 2020, 10, 1902783).

2) Partially replacing Cl with O can dramatically increase the ionic conductivities in Li-
Ta-O-Cl system. This is probably related to the strong electronegativity of O anions. We already proved in our manuscript that O mainly acts as bridges to connect Ta-centered polyhedrons (Fig.  3 in the manuscript). The electron distribution of O-Ta-Cl in Li-Ta-O-Cl materials is more asymmetric than the Cl-Ta-Cl in Li-Ta-Cl materials, leading to weak Coulombic forces between terminal Cl and Li. As a result, Li ions could be easier to escape from one site and jump to another. Besides, oxygens at the bridging positions can enlarge the doorway radius for easy access of Li ions (J. Phys. Chem. B 2006, 110, 16318-16325).

3) O substitution decreases the activation energies of Li-Ta-Cl
. This is because the bridging oxygen networks can induce a much wider range of distortions in Li sites, which are the predominance to realize a Li-ion energy landscape with low migration energy (Nat. Mater. 2022,   21, 1-8).
In the current manuscript, we explained the benefits of oxygen incorporation (see below the quote/paste sentences from the last paragraph of Page 14 in the manuscript).
'…corner-shared oxygen (O-2Ta) networks could induce a much wider range of distortions in Li sites. 57 The distorted lithium sites in O-2Ta networks were the predominance to realize a Li-ion energy landscape with low migration energy. At the same time, oxygens at the bridging positions would enlarge the doorway radius for easy access of Li ions. 58 Third, the unsaturated Ta-Cl···Li bonds in [TaCl5-aOa] a-(1 ≤ a < 5) showed weak Coulombic forces between lithium and chlorine, making it easier for Li ions escape from one site and jump to another…' In order to emphasize and fully support this point, we updated the descriptions in the revised manuscript and added the XRD and EIS data of chloride-based Li3.2TaCl8.2 in the revised supplementary information.

Revision made:
We have added one figure in the revised supplementary information as Supplementary Fig. 12. The following sentences have been updated in the revised manuscript.
Page 14 in the revised manuscript: '…making it easier for Li ions escape from one site and jump to another. In short, oxygen incorporation is beneficial to the amorphization of xLi2O-TaCl5. The induced disordered structures in amorphous xLi2O-TaCl5 lead to a sharply increased ionic conductivity and decreased activation energy compared to the single-anion Li-Ta-Cl sample (see comparison data in Supplementary Fig. 12).' Page 8-9 in the revised supplementary information: Supplementary Fig. 12 A Li-Ta-Cl sample without O incorporation was prepared following the same experimental procedure for xLi2O-TaCl5. The composition of Li3.2TaCl8.2 was chosen for the same Li/Ta ratio as the most conductive 1.6Li2O-TaCl5 amorphous SE: (a) Lab-based XRD patterns for the as-prepared Li3.2TaCl8.2. The hump between 10 o and 30 o is the diffraction peak of the Kapton film which was used to protect the sample from air exposure. The diffraction peaks can be assigned to the TaCl5 and LiCl raw materials. (b) Nyquist plots and (c) Arrhenius plot for the Li3.2TaCl8.2 pellet at various temperatures. Overall, without O incorporation, the completed amorphization of Li-Ta-Cl would be difficult. The RT ionic conductivity of Li3.2TaCl8.2 dropped to the order of 10 -7 S cm -1 with a significantly increased activation energy of 0.546 eV.
2. How the authors determined that the observed conductivity is "ionic conductivity"? The author should show the transport number of electronic conduction, ionic conduction, and Li-ion conduction.
Response: We sincerely appreciate the reviewer for this question, which makes the data description in the revised manuscript more accurate. Indeed, the value derived from the EIS test could be roughly regarded as ionic conductivity only if the charge carriers in the tested SEs are Li ions (Acc. Mater. Res. 2021, 2, 869−880). In our manuscript, other characterizations are needed to prove the reported amorphous SEs are not only electron insulators but also good Li-ion conductors. During the revision, we performed direct current (DC) measurements of 1.6Li2O-TaCl5 and 1.5Li2O-HfCl4 pellets under ion-blocking condition ( Figure R5a) and electronblocking condition (Figure R5f) to calculate the effective electronic and Li-ion conductivities, respectively (Energy Environ. Sci.,2023, 16, 610;Adv. Mater. 2018, 30, 1803075). As shown in Figure R5b and d, a constant voltage was applied to an ion-blocking symmetric cell for an hour until the cell polarization reached equilibrium. The stabilized current responses were then recorded at different voltages from 0.1 V to 0.5 V (Figure R5c and e). The electron conductivity (σe-) of 1.6Li2O-TaCl5 or 1.5Li2O-HfCl4 can be determined by Equation 1: where d is the thickness of the 1.6Li2O-TaCl5 or 1.5Li2O-HfCl4 pellet (between 0.04 cm and 0.06 cm), A is the geometric area of the pellet, and Re-can be obtained via Ohm's Law from Figure   R5c and e. As a result, the electronic conductivity was 3.37 × 10 -10 S cm -1 for 1.6Li2O-TaCl5 and 1.57× 10 -10 S cm -1 for 1.5Li2O-HfCl4, which were seven orders of magnitude lower than the EIS conductivity values. Therefore, electron transport in both1.6Li2O-TaCl5 and 1.5Li2O-HfCl4 can be considered negligible.
We further verified the conducting carriers in 1.6Li2O-TaCl5 and 1.5Li2O-HfCl4 via the similar DC measurement but with a different cell configuration (Figure R5f). In this case, 1.6Li2O-TaCl5 or 1.5Li2O-HfCl4 was sandwiched by Li6PS5Cl SE and Li metal. Since Li6PS5Cl is known as a Li-ion conductor, this cell configuration can block electrons as well as other ion species (such as Cl and O ions) and only allow the access of Li ions. As shown in Figure R5g-j, the polarized current response was recorded under different bias voltages. The total Li-ion resistance (RLi+) can be obtained as 65.12 for 1.6Li2O-TaCl5-contained cell and 99.09 for 1.5Li2O-HfCl4-contained cell. To subtract the additional resistance contributions from the Li6PS5Cl SE and Li metal, a symmetric cell of Li/Li6PS5Cl/Li was also constructed (RLi6PS5Cl SE + Li = 53.87 ). Finally, a DC Li-ion conductivity (σLi+) was calculated to be 6.35 × 10 -3 S cm -1 for 1.6Li2O-TaCl5 and 1.67 × 10 -3 S cm -1 for 1.5Li2O-HfCl4, which was consistent with those from the EIS measurement. The small differences (1.6Li2O-TaCl5: 6.35 × 10 -3 S cm -1 (DC) vs.
Based on above results, we can identify that xLi2O-MCly (M = Ta or Hf, 0.8 ≤ x ≤ 2, y = 5 or 4) amorphous SEs are pure Li-ion conductors. The observed ionic conductivity via EIS test can be regarded as the Li-ion conductivity for each of the compound. Similarly, (f) shows the electron-blocking cell configuration while (g-j) present the DC polarization results.

Revision made:
In response to the reviewer's concern, we have added the Figure R5 and relevant description in the revised supplementary information as Supplementary Fig. 7. The following descriptions, measurements, and references have also been updated in the revised manuscript.
Page 7 in the revised manuscript: '…The 1.5Li2O-HfCl4 SE in mostly amorphous state showed the highest ionic conductivity (1.97 × 10 -3 S cm -1 ) and a low activation energy (0.328 eV) among the xLi2O-HfCl4 series ( Fig. 2d and   Supplementary Fig. 6). Direct current (DC) measurements for the representative 1.6Li2O-TaCl5 and 1.5Li2O-HfCl4 amorphous SEs under ion-blocking and electron-blocking conditions 13,32 were also conducted as shown in Supplementary Fig. 7. The determined electronic conductivities were negligible (at 10 -10 S cm -1 order). The Li-ion conductivities calculated from the DC measurements agree well with the values we derived from the EIS measurements, confirming the xLi2O-MCly amorphous SEs as excellent Li-ion conductors.' …The applied frequency range was 1 Hz ~ 7 MHz and the voltage amplitude was 20 mV. The cell assembly process for DC measurements was similar with that for EIS test. To determine the electronic conductivity, the current responses of the cell was measured at a range of constant voltages for 60 min each. The applied voltage ranged from 0.1 to 0.5 V with a step size of 0.1 V. The DC Li-ion conductivity was evaluated with a symmetric cell configuration of Li/Li6PS5Cl/xLi2O-MCly/Li6PS5Cl/Li under a bias voltage for 30 min. The bias voltage was applied at 5, 10, 15, 20, and 25 mV consecutively. The Li6PS5Cl SE (provided by China Automotive Battery Research Institute Co, Ltd) was used to prevent direct contact between Li metal and xLi2O-MCly SE. ' 4. In the low-temperature charge-discharge test, the authors described that LGPS was used. The cell configuration was Li-In/LGPS/xLi2O-TaCl5/LiCoO2? Anyway, the electrochemical window of the present solid electrolytes should be discussed.

Response:
We highly appreciate the reviewer for this comment. In the low-temperature chargedischarge test, we used LGPS interlayer between 1.6Li2O-TaCl5 and Li-In anode to prevent the direct contact of 1.6Li2O-TaCl5 and Li-In anode, and at the same time, decrease the total cell resistance at the low-temperature testing environment. We have added the cell configuration information (such as Li-In/Li3YCl6/xLi2O-MCly/NCM83 and Li-In/LGPS/xLi2O-MCly/LCO) in the corresponding figures (see the response for Question 3 from Reviewer #2).
We totally agree with the reviewer that electrochemical stability window (ESW) of an SE is important and should be provided. During the revision process, we tested the ESWs of two representative amorphous SEs: 1.6Li2O-TaCl5 and 1.5Li2O-HfCl4. As shown in Figure R6, the ESWs of 1.6Li2O-TaCl5 and 1.5Li2O-HfCl4 are 2.20 V-4.15 V and 2.10 V-4.10 V (vs. Li + /Li). Since the cathodic limit of both two types of amorphous SEs is higher than 2 V, we choose Li3YCl6 or LGPS as interlayer to separate amorphous SE and Li-In anode in ASSBs. Similar strategies have been widely used for the halide-based ASSBs (Energy Environ. Sci., 2020, 13, 2056−2063Nat. Energy 2022, 7, 83−93;Nat. Commun. 2021, 12, 4410).

Revision made:
In response to the reviewer's concerns, we have added the Figure R6 in the revised supplementary information as Supplementary Fig. 16. The following sentences and LSV test method have also been updated in the revised manuscript.